1,3-Bis{[(2,6-di­methyl­phen­yl)sulfan­yl]meth­yl}benzene

Garita-Salazar, B.; Pineda, L.W.

doi:10.1107/S2414314619006771

organic compounds

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ISSN: 2414-3146

Volume 4| Part 5| May 2019| x190677

https://doi.org/10.1107/S2414314619006771

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1,3-Bis{[(2,6-dimethylphenyl)sulfanyl]methyl}benzene

Bruno Garita-Salazar ^a,^b and Leslie W. Pineda ^a,^b ^*

^aCentro de Electroquímica y Energía Química (CELEQ), Universidad de Costa Rica, 11501, San José, Costa Rica, and ^bEscuela de Química, Universidad de Costa Rica, 11501, San José, Costa Rica
^*Correspondence e-mail: leslie.pineda@ucr.ac.cr

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 8 April 2019; accepted 12 May 2019; online 24 May 2019)

The structure of the title compound, C₂₄H₂₆S₂, an example of a pincer ligand with an SCS-chelation motif, illustrates the steric effects of the methyl groups in the thiophenyl rings at the 2- and 6-positions, forcing a dissimilar spatial orientation of the thiophenyl rings relative to the central aryl group [dihedral angles = 33.58 (7) and 40.49 (7)°]. In the crystal, weak S⋯S contacts [3.4009 (7) Å] link the molecules into inversion dimers.

Keywords: crystal structure; chelating ligand; SCS pincer ligands; kinetic stabilization; sulfur atom.

CCDC reference: 1883165

Structure description

Thermodynamic and kinetic stabilization are widely used synthetic concepts for the molecular design of highly reactive species. While the first approach harnesses the mesomeric effect of neighboring heteroatoms, the attachment of electron-donating or -withdrawing substituents or complexation with a transition metal, the second technique takes advantage of steric protection by bulky groups (Tokitoh & Okazaki, 2001 ; Albrecht et al., 2001 ). In this context, pincer-type ligands consisting of a planar aryl backbone (common framework) and two neutral donor groups, result in an ECE chelating environment (E = 2-electron donor atom; C = ipso carbon atom of the aromatic scaffold). Such tridentate ligands have been commonly employed to generate versatile organic and organometallic systems rich in electrons with tunable features, leading to several applications in homogeneous catalysis, activation of strong bonds or as potential therapeutic and pharmaceutical agents (Morales-Morales & Jensen, 2007 ). For instance, monoanionic aromatic ligands containing one or two ortho-pendant functional group(s), bearing intramolecularly coordinating chelating ligands (Dostál et al., 2006 ) (E = N, P, O, S, Se) and bonded with aryl or aliphatic substituents, stabilized both transition-metal and main-group complexes affording direct metal-to-carbon σ-bonds, and delivering hypervalent or hypercoordinated compounds (Jambor et al., 2002 ). In effect, the modification of the electronic properties by donor atoms enhances the nucleophilicity significantly, along with changes in the spatial arrangement by the stereochemical configuration and rigidity of the carbon chain connecting these donor atoms (van Koten et al., 1989 ), as well the solubility (Šimon et al., 2010 ). As part of our studies in this area, we now report the synthesis and structure of the title compound, C₂₄H₂₆S₂.

The crystal structure of the title compound has monoclinic symmetry with one molecule in the asymmetric unit: the central phenyl ring (C1–C6) is bonded to methylene moieties (C7 and C16) at the 2- and 6-positions and these latter fragments further act as bridges to the thiophenyl rings (Fig. 1). The thiophenyl rings are each flanked by a pair of methyl groups (C14, C15, C23, and C24) at the 2- and 6-positions, and show dissimilar spatial orientations, being farther away from each other in relation to the central aryl backbone. Such an arrangement is likely due to steric effects of the methyl groups and the rotation around the C_m—S (m = methylene) bond. The bond lengths C7—S2 and C16—S1 are 1.839 (2) and 1.834 (2) Å, respectively. The corresponding methylene/thiophenyl units (C7—S2—C8 and C16—S1—C17) exhibit bond angles of 100.76 (7) and 101.96 (7)°, respectively. In the crystal, weak S2⋯S2ⁱ contacts [3.4009 (7) Å; symmetry code: (i) 1 – x, 1 – y, 1 – z] are observed between the molecules, leading to the formation of inversion dimers (Fig. 2).

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

Figure 2
Partial packing diagram for the title compound. S2⋯S2 interactions are shown as blue dashed lines.

Synthesis and crystallization

All manipulations were carried out using standard Schlenk techniques or in a glovebox (Lab MBraun workstation) under a nitrogen atmosphere. All reagents and solvents were procured from commercial sources. Anhydrous solvents were dried as reported in the literature.

The title compound was synthesized according to a literature procedure (Romero et al., 1996 ) with some modifications. In a three-neck flask, a solution of 85% KOH solution in n-butanol (100 mL) [KOH (1.88 g, 28.50 mmol) as pellets was dried under vacuum for 1 h and dissolved in n-butanol (100 mL)] and 2,6-dimethylthiophenol (3.80 mL, 28.50 mmol) were mixed and refluxed for 30 min under nitrogen protection, giving a light-yellow solution. While the reaction mixture was still hot, a colourless solution of 1,3-bis(bromomethyl)benzene (3.75 g, 14.25 mmol) in n-butanol (90 mL) was added, and it was further refluxed for 1 h. At this stage, the reaction mixture turned off-white due to the formation of KBr, which was afterward filtered off while still hot. The resulting filtrate was allowed to stand in a water bath at ambient temperature to crystallize slowly. On cooling, after 2 d a white crystalline solid of the title compound was precipitated. It was filtered off, washed with distilled water to dissolve any remaining KBr (2 × 100 mL) and cold n-butanol (2 × 20 mL), and dried under vacuum. Yield: 2.42 g (45%) m.p. 357–358 K, ¹H NMR (400 MHz, CDCl₃, 298 K): δ 7.08–7.15 (m, 7H), 6.96 (d, 2H), 6.69 (s, 1H), (3.70 (s, 4H), 2.40 p.p.m. (s, 6H). ¹³C NMR NMR (400 MHz, CDCl₃, 298 K): δ 143.5, 138.3, 132.9, 129.3, 128.4, 128.3, 128.0, 127.3, 39.6, 21.8 p.p.m. ¹H NMR and ¹³C NMR are given in the supporting information Colourless blocks of the title compound were grown from a warm saturated n-butanol solution upon cooling in a water bath at ambient temperature.

Refinement

Crystal data, data collection ans structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₂₄H₂₆S₂
M_r	378.57
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	8.4487 (2), 23.7284 (5), 10.4078 (2)
β (°)	104.698 (1)
V (Å³)	2018.22 (8)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	2.40
Crystal size (mm)	0.25 × 0.15 × 0.10

Data collection
Diffractometer	Bruker D8 Venture
Absorption correction	Multi-scan (SADABS; Bruker, 2015 )
T_min, T_max	0.630, 0.753
No. of measured, independent and observed [I > 2σ(I)] reflections	30031, 3679, 3342
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.077, 1.05
No. of reflections	3679
No. of parameters	239
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.26
Computer programs: APEX3 and SAINT (Bruker, 2015), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), shelXle (Hübschle et al., 2011 and Mecury (Macrae et al., 2006 ).

Structural data

CCDC reference: 1883165

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314619006771/hb4295sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619006771/hb4295Isup2.hkl

1H NMR 13C NMR. DOI: https://doi.org/10.1107/S2414314619006771/hb4295sup3.docx

Supporting information file. DOI: https://doi.org/10.1107/S2414314619006771/hb4295Isup4.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: shelXle (Hübschle et al., 2011 and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).

1,3-Bis{[(2,6-dimethylphenyl)sulfanyl]methyl}benzene top

Crystal data top

C₂₄H₂₆S₂	F(000) = 808
M_r = 378.57	D_x = 1.246 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
a = 8.4487 (2) Å	Cell parameters from 9984 reflections
b = 23.7284 (5) Å	θ = 3.7–68.2°
c = 10.4078 (2) Å	µ = 2.40 mm⁻¹
β = 104.698 (1)°	T = 100 K
V = 2018.22 (8) Å³	Block, colourless
Z = 4	0.25 × 0.15 × 0.10 mm

Data collection top

Bruker D8 Venture diffractometer	3679 independent reflections
Radiation source: Incoatec microsource	3342 reflections with I > 2σ(I)
Mirrors monochromator	R_int = 0.038
Detector resolution: 10.4167 pixels mm^-1	θ_max = 68.3°, θ_min = 3.7°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −28→28
T_min = 0.630, T_max = 0.753	l = −12→12
30031 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.036P)² + 0.9617P] where P = (F_o² + 2F_c²)/3
3679 reflections	(Δ/σ)_max = 0.002
239 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. All hydrogen atoms were placed geometrically and refined using a riding-atom model approximation, with C—H = 0.95–1.00 Å and U_iso(H) = 1.2U_eq(C). A rotating model was used for the methyl groups.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	−0.05299 (4)	0.78989 (2)	0.46396 (3)	0.02099 (10)
C1	0.26784 (17)	0.68696 (6)	0.52695 (14)	0.0184 (3)
H1	0.2166	0.6767	0.4379	0.022*
S2	0.52713 (4)	0.57105 (2)	0.50641 (3)	0.02155 (10)
C2	0.17461 (17)	0.71129 (6)	0.60489 (14)	0.0192 (3)
C5	0.50961 (18)	0.69337 (6)	0.70751 (15)	0.0215 (3)
H5	0.6237	0.6877	0.7426	0.026*
C4	0.41787 (19)	0.71745 (6)	0.78570 (15)	0.0237 (3)
H4	0.4695	0.7283	0.8743	0.028*
C3	0.25039 (19)	0.72598 (6)	0.73568 (15)	0.0223 (3)
H3	0.1878	0.7418	0.7907	0.027*
C6	0.43510 (17)	0.67737 (6)	0.57694 (14)	0.0188 (3)
C7	0.53111 (18)	0.64828 (6)	0.49341 (15)	0.0223 (3)
H7A	0.6461	0.6613	0.5209	0.027*
H7B	0.4863	0.6592	0.3994	0.027*
C8	0.63461 (17)	0.56138 (6)	0.67620 (14)	0.0182 (3)
C9	0.54664 (17)	0.55204 (6)	0.77163 (15)	0.0201 (3)
C10	0.63401 (19)	0.54523 (6)	0.90400 (15)	0.0238 (3)
H10	0.5763	0.5393	0.9702	0.029*
C11	0.80332 (19)	0.54693 (6)	0.94022 (15)	0.0253 (3)
H11	0.8608	0.5423	1.0307	0.03*
C12	0.88842 (18)	0.55536 (6)	0.84522 (15)	0.0235 (3)
H12	1.0046	0.5563	0.8709	0.028*
C13	0.80697 (17)	0.56250 (6)	0.71206 (15)	0.0199 (3)
C14	0.90487 (19)	0.57030 (7)	0.61095 (17)	0.0291 (4)
H14A	0.8624	0.5452	0.5352	0.044*
H14B	1.0199	0.5613	0.6514	0.044*
H14C	0.896	0.6095	0.5804	0.044*
C15	0.36202 (18)	0.54935 (7)	0.73663 (17)	0.0275 (3)
H15A	0.3168	0.586	0.7022	0.041*
H15B	0.3255	0.54	0.8162	0.041*
H15C	0.324	0.5203	0.6688	0.041*
C16	−0.00542 (18)	0.72194 (6)	0.54890 (15)	0.0222 (3)
H16A	−0.0605	0.7202	0.6222	0.027*
H16B	−0.0512	0.6914	0.4854	0.027*
C17	−0.00375 (17)	0.83831 (6)	0.59923 (14)	0.0180 (3)
C18	−0.11909 (17)	0.84889 (6)	0.67253 (14)	0.0206 (3)
C19	−0.0832 (2)	0.88954 (6)	0.77240 (15)	0.0248 (3)
H19	−0.1594	0.8968	0.8236	0.03*
C20	0.0622 (2)	0.91949 (7)	0.79792 (15)	0.0277 (4)
H20	0.0854	0.9469	0.8666	0.033*
C21	0.17354 (19)	0.90944 (6)	0.72361 (15)	0.0250 (3)
H21	0.272	0.9307	0.7408	0.03*
C22	0.14412 (17)	0.86870 (6)	0.62377 (14)	0.0202 (3)
C23	0.26849 (18)	0.85884 (7)	0.54506 (17)	0.0275 (4)
H23A	0.2162	0.8632	0.4502	0.041*
H23B	0.3127	0.8206	0.5619	0.041*
H23C	0.3575	0.8863	0.5719	0.041*
C24	−0.28224 (19)	0.81941 (7)	0.64360 (18)	0.0321 (4)
H24A	−0.3467	0.8298	0.5545	0.048*
H24B	−0.3411	0.8307	0.7094	0.048*
H24C	−0.2651	0.7785	0.6481	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02004 (18)	0.02104 (19)	0.01986 (18)	0.00211 (13)	0.00130 (14)	−0.00266 (14)
C1	0.0220 (7)	0.0146 (7)	0.0173 (7)	−0.0007 (5)	0.0023 (6)	0.0011 (5)
S2	0.02313 (19)	0.02071 (19)	0.01796 (18)	0.00424 (14)	−0.00004 (14)	−0.00098 (14)
C2	0.0221 (7)	0.0133 (7)	0.0223 (7)	−0.0008 (5)	0.0057 (6)	0.0014 (6)
C5	0.0212 (7)	0.0170 (7)	0.0234 (7)	−0.0019 (6)	0.0001 (6)	0.0029 (6)
C4	0.0324 (8)	0.0190 (8)	0.0166 (7)	−0.0020 (6)	0.0003 (6)	−0.0006 (6)
C3	0.0304 (8)	0.0173 (7)	0.0206 (7)	0.0007 (6)	0.0091 (6)	−0.0010 (6)
C6	0.0219 (7)	0.0142 (7)	0.0205 (7)	−0.0001 (5)	0.0056 (6)	0.0037 (5)
C7	0.0226 (7)	0.0225 (8)	0.0215 (7)	0.0028 (6)	0.0049 (6)	0.0050 (6)
C8	0.0186 (7)	0.0145 (7)	0.0198 (7)	0.0015 (5)	0.0019 (6)	−0.0014 (6)
C9	0.0207 (7)	0.0149 (7)	0.0248 (7)	0.0006 (5)	0.0059 (6)	−0.0008 (6)
C10	0.0340 (8)	0.0189 (8)	0.0205 (7)	0.0004 (6)	0.0106 (6)	−0.0005 (6)
C11	0.0327 (8)	0.0185 (8)	0.0199 (7)	0.0019 (6)	−0.0023 (6)	−0.0012 (6)
C12	0.0196 (7)	0.0182 (7)	0.0283 (8)	−0.0001 (6)	−0.0019 (6)	−0.0003 (6)
C13	0.0192 (7)	0.0147 (7)	0.0253 (8)	0.0008 (5)	0.0045 (6)	0.0010 (6)
C14	0.0222 (8)	0.0301 (9)	0.0368 (9)	0.0034 (6)	0.0109 (7)	0.0082 (7)
C15	0.0209 (8)	0.0289 (9)	0.0349 (9)	−0.0004 (6)	0.0110 (7)	0.0003 (7)
C16	0.0216 (7)	0.0168 (7)	0.0281 (8)	−0.0015 (6)	0.0064 (6)	−0.0030 (6)
C17	0.0184 (7)	0.0165 (7)	0.0174 (7)	0.0026 (5)	0.0014 (6)	0.0018 (5)
C18	0.0214 (7)	0.0182 (7)	0.0219 (7)	0.0034 (6)	0.0048 (6)	0.0037 (6)
C19	0.0346 (8)	0.0220 (8)	0.0189 (7)	0.0062 (6)	0.0088 (6)	0.0031 (6)
C20	0.0422 (9)	0.0184 (8)	0.0185 (7)	0.0012 (7)	0.0006 (7)	0.0001 (6)
C21	0.0261 (8)	0.0197 (8)	0.0237 (8)	−0.0033 (6)	−0.0038 (6)	0.0046 (6)
C22	0.0187 (7)	0.0184 (7)	0.0213 (7)	0.0017 (6)	0.0007 (6)	0.0059 (6)
C23	0.0187 (7)	0.0276 (9)	0.0359 (9)	−0.0005 (6)	0.0066 (7)	0.0040 (7)
C24	0.0234 (8)	0.0324 (9)	0.0443 (10)	−0.0013 (7)	0.0155 (7)	−0.0036 (8)

Geometric parameters (Å, º) top

S1—C17	1.7827 (14)	C12—H12	0.95
S1—C16	1.8337 (15)	C13—C14	1.506 (2)
C1—C2	1.391 (2)	C14—H14A	0.98
C1—C6	1.395 (2)	C14—H14B	0.98
C1—H1	0.95	C14—H14C	0.98
S2—C8	1.7848 (14)	C15—H15A	0.98
S2—C7	1.8385 (15)	C15—H15B	0.98
C2—C3	1.394 (2)	C15—H15C	0.98
C2—C16	1.506 (2)	C16—H16A	0.99
C5—C4	1.382 (2)	C16—H16B	0.99
C5—C6	1.398 (2)	C17—C18	1.404 (2)
C5—H5	0.95	C17—C22	1.409 (2)
C4—C3	1.393 (2)	C18—C19	1.394 (2)
C4—H4	0.95	C18—C24	1.506 (2)
C3—H3	0.95	C19—C20	1.385 (2)
C6—C7	1.499 (2)	C19—H19	0.95
C7—H7A	0.99	C20—C21	1.381 (2)
C7—H7B	0.99	C20—H20	0.95
C8—C9	1.401 (2)	C21—C22	1.395 (2)
C8—C13	1.409 (2)	C21—H21	0.95
C9—C10	1.397 (2)	C22—C23	1.506 (2)
C9—C15	1.510 (2)	C23—H23A	0.98
C10—C11	1.384 (2)	C23—H23B	0.98
C10—H10	0.95	C23—H23C	0.98
C11—C12	1.377 (2)	C24—H24A	0.98
C11—H11	0.95	C24—H24B	0.98
C12—C13	1.392 (2)	C24—H24C	0.98

C17—S1—C16	101.96 (7)	H14A—C14—H14B	109.5
C2—C1—C6	121.33 (13)	C13—C14—H14C	109.5
C2—C1—H1	119.3	H14A—C14—H14C	109.5
C6—C1—H1	119.3	H14B—C14—H14C	109.5
C8—S2—C7	100.76 (7)	C9—C15—H15A	109.5
C1—C2—C3	119.04 (13)	C9—C15—H15B	109.5
C1—C2—C16	120.64 (13)	H15A—C15—H15B	109.5
C3—C2—C16	120.31 (13)	C9—C15—H15C	109.5
C4—C5—C6	120.23 (14)	H15A—C15—H15C	109.5
C4—C5—H5	119.9	H15B—C15—H15C	109.5
C6—C5—H5	119.9	C2—C16—S1	114.23 (10)
C5—C4—C3	120.55 (14)	C2—C16—H16A	108.7
C5—C4—H4	119.7	S1—C16—H16A	108.7
C3—C4—H4	119.7	C2—C16—H16B	108.7
C4—C3—C2	120.01 (14)	S1—C16—H16B	108.7
C4—C3—H3	120.0	H16A—C16—H16B	107.6
C2—C3—H3	120.0	C18—C17—C22	121.05 (13)
C1—C6—C5	118.82 (14)	C18—C17—S1	119.29 (11)
C1—C6—C7	120.31 (13)	C22—C17—S1	119.45 (11)
C5—C6—C7	120.82 (13)	C19—C18—C17	118.62 (14)
C6—C7—S2	113.18 (10)	C19—C18—C24	119.04 (14)
C6—C7—H7A	108.9	C17—C18—C24	122.30 (14)
S2—C7—H7A	108.9	C20—C19—C18	120.84 (15)
C6—C7—H7B	108.9	C20—C19—H19	119.6
S2—C7—H7B	108.9	C18—C19—H19	119.6
H7A—C7—H7B	107.8	C21—C20—C19	120.05 (14)
C9—C8—C13	120.92 (13)	C21—C20—H20	120.0
C9—C8—S2	119.61 (11)	C19—C20—H20	120.0
C13—C8—S2	119.47 (11)	C20—C21—C22	121.25 (14)
C10—C9—C8	118.34 (13)	C20—C21—H21	119.4
C10—C9—C15	119.19 (14)	C22—C21—H21	119.4
C8—C9—C15	122.47 (13)	C21—C22—C17	118.17 (14)
C11—C10—C9	121.07 (14)	C21—C22—C23	119.73 (14)
C11—C10—H10	119.5	C17—C22—C23	122.09 (13)
C9—C10—H10	119.5	C22—C23—H23A	109.5
C12—C11—C10	120.03 (14)	C22—C23—H23B	109.5
C12—C11—H11	120.0	H23A—C23—H23B	109.5
C10—C11—H11	120.0	C22—C23—H23C	109.5
C11—C12—C13	121.08 (14)	H23A—C23—H23C	109.5
C11—C12—H12	119.5	H23B—C23—H23C	109.5
C13—C12—H12	119.5	C18—C24—H24A	109.5
C12—C13—C8	118.55 (14)	C18—C24—H24B	109.5
C12—C13—C14	119.35 (13)	H24A—C24—H24B	109.5
C8—C13—C14	122.09 (13)	C18—C24—H24C	109.5
C13—C14—H14A	109.5	H24A—C24—H24C	109.5
C13—C14—H14B	109.5	H24B—C24—H24C	109.5

C6—C1—C2—C3	−0.4 (2)	C11—C12—C13—C14	−178.63 (14)
C6—C1—C2—C16	179.32 (13)	C9—C8—C13—C12	−1.4 (2)
C6—C5—C4—C3	0.1 (2)	S2—C8—C13—C12	179.45 (11)
C5—C4—C3—C2	−1.4 (2)	C9—C8—C13—C14	177.68 (14)
C1—C2—C3—C4	1.5 (2)	S2—C8—C13—C14	−1.43 (19)
C16—C2—C3—C4	−178.22 (13)	C1—C2—C16—S1	−87.22 (15)
C2—C1—C6—C5	−0.8 (2)	C3—C2—C16—S1	92.49 (15)
C2—C1—C6—C7	176.71 (13)	C17—S1—C16—C2	−70.83 (12)
C4—C5—C6—C1	1.0 (2)	C16—S1—C17—C18	−82.68 (12)
C4—C5—C6—C7	−176.56 (13)	C16—S1—C17—C22	102.54 (12)
C1—C6—C7—S2	−86.79 (15)	C22—C17—C18—C19	−1.2 (2)
C5—C6—C7—S2	90.70 (15)	S1—C17—C18—C19	−175.88 (11)
C8—S2—C7—C6	−65.52 (12)	C22—C17—C18—C24	176.53 (14)
C7—S2—C8—C9	99.48 (12)	S1—C17—C18—C24	1.8 (2)
C7—S2—C8—C13	−81.39 (12)	C17—C18—C19—C20	0.8 (2)
C13—C8—C9—C10	1.6 (2)	C24—C18—C19—C20	−176.95 (14)
S2—C8—C9—C10	−179.31 (11)	C18—C19—C20—C21	0.3 (2)
C13—C8—C9—C15	−178.71 (14)	C19—C20—C21—C22	−1.1 (2)
S2—C8—C9—C15	0.41 (19)	C20—C21—C22—C17	0.8 (2)
C8—C9—C10—C11	−0.8 (2)	C20—C21—C22—C23	−179.86 (14)
C15—C9—C10—C11	179.46 (14)	C18—C17—C22—C21	0.4 (2)
C9—C10—C11—C12	−0.1 (2)	S1—C17—C22—C21	175.08 (11)
C10—C11—C12—C13	0.2 (2)	C18—C17—C22—C23	−178.95 (13)
C11—C12—C13—C8	0.5 (2)	S1—C17—C22—C23	−4.27 (19)

Acknowledgements

Rectoría and Vicerrectoría de Investigación, Universidad de Costa Rica are acknowledged for funding the purchase of a D8 Venture SC XRD. CELEQ is thanked for supplying liquid nitrogen for the X-ray measurements.

Funding information

Funding for this research was provided by: Centro de Electroquímica y Energía Química (CELEQ), Universidad de Costa Rica (scholarship to Bruno Garita-Salazar); Vicerrectoría de Investigación, Universidad de Costa Rica (grant No. 804-B7-274).

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